CN101896287B

CN101896287B - Method of forming multilayered coating film, multilayered coating film, and coated article

Info

Publication number: CN101896287B
Application number: CN200880120518.1A
Authority: CN
Inventors: 稻田祐一; 增田秀树
Original assignee: Kansai Paint Co Ltd
Current assignee: Kansai Paint Co Ltd
Priority date: 2007-12-13
Filing date: 2008-12-09
Publication date: 2013-06-19
Anticipated expiration: 2028-12-09
Also published as: WO2009075369A1; CN101896287A

Abstract

A method of forming a multilayered coating film which comprises: a step in which a starch-based colored base coating material containing a starch-based resin is applied to a work to be coated to form a coating film; a step in which a photocurable coating material (B) comprising a photocurable compound and/or photocurable resin (b1), a photopolymerization initiator (b2), and a starch-based resin (b3) is applied to that coating film to form a coating film; and a step in which the coating film of the photocurable coating material (B) is irradiated with light to cure this coating film. As the photocurable coating material (A) or (B) is used a coating material based on a starch derived from a vegetable. This method can form a multilayered coating film excellent in finish, pencil hardness, marring resistance, adhesion, alkali resistance, and solvent resistance.

Description

Method of forming layered coating film and multilayer film and coated article

Technical field

The present invention relates to a kind of method of forming layered coating film, it forms and films by being used to starch-series colored base from the starch of plant, forms and films by containing photo-curable coating that specific starch-series resin forms on this is filmed, and make its photocuring.The invention still further relates to multilayer film and contain the coated article of this multilayer film.

Background technology

In recent years, from reducing the viewpoint consideration on the impact of global warming, require to reduce CO by world standard ₂Discharge capacity requires actively to utilize as not increasing CO in carbon dioxide circulation renewable resource, on earth ₂The raw material from plant of discharge capacity.

As so representational material from natural goods; at present relevant to food industry, with the relevant industry of paper industry in use have as modified starches such as the starch of polysaccharide or acetylated starches; in recent years; these starch use in the raw material of plastics, at the field goods constantly widely such as food containers, packaging material, fender tablet, plastic film for agricultural use, disposable diaper.

For starch is utilized as the industrial product raw material, in starch conversion, the various improvement of relevant producing starch have constantly been carried out.The basic structure of starch is that alpha-D-glucose passes through 1, the 4-key is with straight chain the shape amylose that links and the mixture with amylopectin of branched structure, in the sixties in last century, carried out gradually carrying out the modifications such as esterification, etherificate by utilizing in structure with hydroxyl.

Unexamined Patent 8-239402 communique discloses a kind of direct method for preparing graft starch, and its Jie makes starch-resin and the indirect grafting of acrylic resin by polyisocyanates, makes the unsaturated monomer free yl graft polymerization on starch or modified starch.

Unexamined Patent 6-207047 communique discloses following invention, that is, as making starch and other example from the resin combination of plant, the blend polymer that starch or modified starch and cellulose derivative group is closed form is used as moulding material.This communique also discloses acrylic acid and light-cured resin, thermosetting resin to the resin combinations such as graft polymers of starch.

Patent existing according to these also show, it itself is known making the starch-series resin that various combination of polymers, combination or grafting form.But, in these existing patents, as the purposes of starch-series resin, all be envisioned for bonding agent, structural material, extrusion molding material, sheet material etc., not open purposes as coating.

In addition, the coating that the starch-series resin is arranged about use, disclose the reaction-curable coating that contains by the curing agent starch composites of the compositions of mixtures of this starch-series resin and curing agent in JP 2004-224887 communique, described curing agent have with starch molecule in contained at least 1 hydroxyl carry out the functional group of complementary interaction, also instruction can be the type of the curing types such as oxidation polymerization curing type, normal temperature cured type, active energy ray-curable.

In addition, JP 2006-282960 communique disclose contain starch, polyisocyanate curing agent, except the resin from plant of starch, be selected from metal complex and β-diketone class, acetoacetic ester, malonate class, β position on ketone with hydroxyl, β position the curing type starch composites that forms with the end-capping reagent in the ester class of hydroxyl with on the aldehydes of hydroxyl and β position.

But, about these starch-series coating, for method of forming layered coating film and the multilayer film of finishability, pencil hardness, marresistance, tack, alkali resistance and solvent resistance excellence, or unknown.

Summary of the invention

The object of the invention is to, provide a kind of use from the starch-series coating of plant and can form the method for forming layered coating film of multilayer film of finishability, pencil hardness, marresistance, tack, alkali resistance and solvent resistance excellence and the multilayer film of these excellent performances.

The inventor etc. have carried out wholwe-hearted research for the problem points of eliminating above-mentioned prior art, found that, can solve such problem by following method of forming layered coating film, described multilayer film formation method comprises: will contain starch-series colored base from the starch-series resin of plant and be coated with and be contained on coated article, and form the step of filming that is formed by the starch-series colored base; Application contains the starch-series resin (a1) of unsaturated group and the photo-curable coating (A) of Photoepolymerizationinitiater initiater (a2) on above-mentioned filming, and forms the step of filming that is formed by photo-curable coating (A); Ethyl carries out irradiation to filming of being formed by photo-curable coating (A), makes the step of this curing of coating.

And then, the discoveries such as the inventor, also can solve such problem by following method of forming layered coating film, thereby completed the present invention, described method of forming layered coating film comprises: will be coated with from the starch-series colored base of plant and be contained on coated article, and form the step of filming that is formed by the starch-series colored base; Application contains the photo-curable coating (B) of photocurable compound and/or light-cured resin (b1), Photoepolymerizationinitiater initiater (b2) and starch-series resin (b3) on above-mentioned filming, and forms the step of filming that is formed by photo-curable coating (B); With filming of being formed by photo-curable coating (B) carried out irradiation, make the step of this curing of coating.

According to method of forming layered coating film of the present invention, because the discharge capacity of the total CO 2 of the life cycle that relates to goods is few, therefore carrying capacity of environment is little, and can form the multilayer film of finishability, pencil hardness, marresistance, tack, alkali resistance and solvent-resisting excellence.

And then, multilayer film of the present invention and coated article, for example plastics parts, because the discharge capacity of the total CO 2 of the life cycle that relates to goods is few, so carrying capacity of environment is little, and finishability, pencil hardness, marresistance, tack, alkali resistance and solvent resistance are excellent.

The specific embodiment

Below, the preferred embodiment of the present invention being described, but wish and can understand, the present invention not merely is defined in these modes, can carry out various distortion in its aim and practical range.

The present invention is the formation method of multilayer film, it comprises: application starch-series colored base on coated article, for example plastics parts and forming is filmed, application contains the photo-curable coating (A) of specific starch-series resin or photo-curable coating (B) and forms and film, and makes its photocuring.Particularly, have the coated article of the multilayer film that utilizes method of forming layered coating film formation of the present invention, be particularly suitable for as plastic products.

Below, at length describe with the order of photo-curable coating (A), photo-curable coating (B).

[photo-curable coating (A)]

The photo-curable coating (A) that is used for method of forming layered coating film of the present invention is to contain the starch-series resin (a1) of unsaturated group and the coating of Photoepolymerizationinitiater initiater (a2).And then, in photo-curable coating (A), with the purpose that rises to of film performance, can contain photocurable compound (a3).

The starch-series resin (a1) that contains unsaturated group:

The starch-series resin (a1) that contains unsaturated group that has unsaturated group in the starch-series resin can obtain by the manufacture method of following grade:

(1) make the hydroxyl of modified starch described later (a10) and the method that unsaturated carboxylic acid (such as acrylic acid, itaconic acid, maleic acid etc.) reacts;

(2) make the hydroxyl composition of the hydroxyl of modified starch (a10) and esters of unsaturated carboxylic acids (such as methyl acrylate, ethyl acrylate, 2-EHA etc.) carry out the method for ester exchange reaction;

(3) make the hydroxyl of modified starch (a10) and the method that unsaturated carbon acyl chlorides (for example, acryloyl chloride) reacts;

(4) make the hydroxyl of modified starch (a10) and contain the method that the unsaturated-resin of NCO reacts;

(5) make the hydroxyl of modified starch (a10) and contain the method that the resin of carboxyl unsaturated group reacts;

(6) the hydroxyl composition that makes the hydroxyl of modified starch (a10) and contain the resin of ester group unsaturated group carries out the method for ester exchange reaction;

Below, illustrate and be specially adapted to the concrete example that contains the starch-series resin (a1) of unsaturated group of the present invention.

The starch-series resin (20) that contains unsaturated group:

As the starch-series resin (a1) that contains unsaturated group, can use suitably modified starch (a10) and the compound (a11) that contains acryloyl group and NCO to react and the starch-series resin (20) that contains unsaturated group that obtains.

Modified starch (a10)

For for the starch of initial substance, can enumerate such as aerial stem of plant unmodified starch such as cornstarch, high amylose starches, wheaten starch, rice starches; The subterranean stem such as farina, tapioca unmodified starch; Dextrin; And the analyte of these starch.Here, as the starch analyte, for example can enumerate: with enzyme, acid or oxidant, starch is implemented the starch analyte of low-molecular-weight processing.As the starch analyte, to consider from making the aspects such as film, number-average molecular weight is preferably 1,000～2, in 000,000, particularly 3,000～500,000, further preferred 3,000～200,000 scope.

So-called modified starch (a10) is to be situated between to be made the organo-functional groups such as sturated aliphatic hydrocarbon base, unsaturated aliphatic hydrocarbon base, aromatic hydrocarbyl be bonded in the modified starch (a10) that forms on starch or starch analyte by ester bond and/or ehter bond.Need to prove, modified starch (a10) can use separately or multiple and use.

Need to prove, in this manual, number-average molecular weight or weight average molecular weight be based on JISK0124-83 record method, use " TSKgel G4000HXL ", " TSKge lG3000HXL ", " TSKge l G2500HXL " to reach " TSKgel G2000HXL " (Jun as pillar to as East ソ one Co., Ltd.'s system, trade name) 4, and use GPC to use oxolane as elutriant, under 40 ℃ of temperature and flow velocity 1.0mL/min, the value of being tried to achieve by the calibration curve of the chromatogram that obtains with the RI refractometer and polystyrene standard.

Need to prove, as the method for modifying of modified starch, can enumerate for example esterification modification, as preferred modified group, can enumerate the acyl group of carbon number 2～18.Modification can by alone or in combination more than 2 kinds the organic acid with carbon number 2～18 carry out.The modification degree of modified starch is preferably in substitution value in 0.5～2.8 scope, is particularly preferably in 1.0～2.5 scope.

At this, substitution value is the mean number that consists of the hydroxyl that the agent that is modified of every monosaccharide units of starch replaces, for example, substitution value 3 refers to consist of 3 hydroxyls that exist in the monosaccharide units of starch agent that all is modified and replaces, and substitution value 1 only refers to consist of in 3 hydroxyls that exist in the monosaccharide units of starch that 1 base that is modified replaces.Lower than 0.5 the time, sometimes insufficient with the compatibility of free-radical polymerised unsaturated monomer described later when substitution value, form the finishability of filming etc. insufficient.On the other hand, when substitution value surpassed 2.8, finishability descended sometimes.

in addition, modified starch has vitrification point below the decomposition temperature (approximately 350 ℃) of starch, wish to regulate the degree of modification so that have thermoplasticity and also have finishability, therefore, in the situation that it is many to be used for the substituent carbon number of modification, for example in the situation that substituting group is the stearyl of carbon number 18, preferred low modification levels, for example making the ester substitution value is in 0.1～1.8 scope, in addition in the situation that substituent carbon number is few, in the situation that substituting group is the acetyl group of carbon number 2, preferred high modification levels, for example making the ester substitution value is in 1.5～2.8 scope.

As the example of modified starch, can enumerate: by being that anhydrous starch more than 50% mixes with esterifying reagent in non-protonic solvent and react the hydrophobic Biodegradable starch ester products (with reference to the flat 8-502552 communique of special table) that obtains between starch and esterifying reagent with amylose content; Be 2～18 vinyl esters for using vinyl esters to carry out starch ester that modification forms, use the carbon number of ester group as this vinyl esters as esterifying reagent, use esterification catalyst to make itself and starch reaction in non-aqueous organic solvent and the starch ester (with reference to Unexamined Patent 8-188601 communique) that obtains; Carry out the starch (with reference to Unexamined Patent 8-239402 communique and Unexamined Patent 8-301994 communique) of the grafting of polyvinylesters in esterification; Part or all that evenly has hydroxyl that polyester grafted chain, this grafted chain end and starch directly links on the mixing starch molecule by ester terminated polyester glycerol polymerization starch with have with part or all of the identical constituent of this polyester grafted chain, terminal hydroxyl by the polyester glycerol polymerization starch alloy (with reference to Unexamined Patent 9-31308 communique) of ester terminated independent polyester etc.

And then, can enumerate: replace the short chain that the hydrogen of the reactive hydroxyl of same starch molecule forms-long-chain mixing starch ester (with reference to JP 2000-159801 communique) with the long acyl of the short chain acyl of carbon number 2～4 and carbon number 6～18; Replace the short chain that the reactive hydroxyl of same starch molecule forms-long-chain mixing starch substitutive derivative (with reference to JP 2000-159802 communique) etc. with the group of the short hydrocarbon that contains carbon number 2～4 and the group that contains the long chain hydrocarbon of carbon number 6～24.These modified starches due to take starch as matrix, be therefore from plant, in addition, and the dissolubility of solvent, compatibility excellence.

The compound (a11) that contains acryloyl group and NCO

As the compound that contains acryloyl group and NCO (a11), can enumerate: the reactant of hydroxy acryl acid ester and polyisocyanate compound, 2-acryloxy ethyl isocyanate etc.

The reactant of above-mentioned hydroxy acryl acid ester and polyisocyanate compound, can obtain by following method etc., namely, in polyisocyanate compound, mix bit by bit hydroxy acryl acid ester (for example hydroxy-ethyl acrylate, acrylic acid hydroxy butyl ester), in the moment of the NCO of the polyisocyanate compound that has consumed the amount of hydroxyl groups that is equivalent to the hydroxy acryl acid ester, stop reaction.as polyisocyanate compound, can enumerate: IPDI, toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, the tolidine vulcabond, naphthalene diisocyanate, triphenylmethane triisocyanate, three (phenyl isocyanate) thiophosphate, phenylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, LDI, the xyxylene vulcabond, two (isocyanato-methyl) cyclohexane, two (isocyanato-) hexahydrotoluene, dicyclohexyl methyl hydride diisocyanate, isopropylidene two (cyclohexyl isocyanate), 3-(2 '-isocyanato-cyclohexyl) propyl group isocyanates, dianisidine diisocyanate, diphenyl ether vulcabond etc.

need to prove, the starch-series resin (20) that contains unsaturated group, can obtain by the following method, namely, modified starch (a10) is mixed in following organic solvent with the compound that contains acryloyl group and NCO (a11), suitably add Mono-n-butyltin, the catalyst such as Dibutyltin oxide, under agitation, at approximately 50 ℃～200 ℃, more preferably make it carry out addition reaction 30 minutes～10 hours at the temperature of 60～150 ℃, more preferably about 1～5 hour, wherein, described modified starch (a10) with the use level that contains the compound (a11) of acryloyl group and NCO is, take modified starch (a10) with the total solid composition quality of compound (a11) that contains acryloyl group and NCO as benchmark, modified starch (a10) is 50～99 quality %, the scope of preferred 60～98 quality %, the compound (a11) that contains acryloyl group and NCO is 1～50 quality %, the scope of preferred 2～40 quality %, described organic solvent such as the hydrocarbon system solvents such as toluene, dimethylbenzene, cyclohexane, n-hexane, the ester series solvents such as methyl acetate, ethyl acetate, butyl acetate, the ketone series solvents such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl amyl ketone, or the mixture of these solvents etc.Need to prove; in order to obtain filming of averaging out aspect finishability, pencil hardness, marresistance, tack, alkali resistance and solvent resistance, preferred modified starch (a10) is in above-mentioned scope with the mixing ratio that contains the compound (a11) of acryloyl group and NCO.

For containing the starch-series resin (20) of unsaturated group, consider from the marresistance of filming, the viewpoint of tack, the scope of preferred number average molecular weight is 3,000～2,000,000, particularly 5,000～100,000, and the scope of hydroxyl value is 0～200mgKOH/g, is preferably 50～150mgKOH/g.

The acrylate of carbohydrate and/or modification carbohydrate (21):

As the starch-series resin (a1) that contains unsaturated group, can use suitably the acrylate (21) of carbohydrate and/or modification carbohydrate.The acrylate (21) of so-called carbohydrate and/or modification carbohydrate refers to carbohydrate and/or modification carbohydrate and acrylic acid ester.

As above-mentioned carbohydrate, can enumerate: the polysaccharides such as starch, cellulose; The starch analytes such as dextrin; Decompose oligosaccharide mixture that compound sugar, disaccharides, monosaccharide and polysaccharide form etc. with acid, enzyme.Wherein, can use suitably maltose.At this, as the modification carbohydrate, can use suitably by at least a kind in the carboxylic acid, carboxylate and the carbonyl halide that are selected from 2～22 of carbon numbers a part of hydroxyl in carbohydrate is carried out the modification carbohydrate that carboxylic esterification forms.

for the manufacturing of the acrylate (21) of carbohydrate and/or modification carbohydrate, carbohydrate and/or modification carbohydrate are mixed in following organic solvent with acrylic acid or acrylate, suitably add alkali compounds, under agitation, at approximately 60 ℃～100 ℃, more preferably make it carry out esterification or ester exchange reaction 30 minutes～10 hours at the temperature of 70～90 ℃, more preferably about 1～5 hour, can obtain the acrylate (21) of carbohydrate and/or modification carbohydrate, wherein, the use level of described carbohydrate and/or modification carbohydrate and acrylic acid or acrylate is, after carbohydrate and/or modification carbohydrate are dissolved in solvent, take the total solid composition quality of acrylic acid or acrylate (for example methyl acrylate) as benchmark, carbohydrate is 50～99 quality %, the scope of preferred 60～98 quality %, acrylic acid or acrylate are 1～50 quality %, the scope of preferred 2～40 quality %, described organic solvent is for example: toluene, dimethylbenzene, cyclohexane, the hydrocarbon system solvents such as n-hexane, the ketone series solvents such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl amyl ketone, or the mixture of these solvents etc.

Other preparation method as the acrylate (21) of carbohydrate and/or modification carbohydrate, can enumerate following method, namely, carbohydrate and/or modification carbohydrate are dissolved in organic solvent, add acryloyl halide (for example acryloyl chloride), (by the desalination acid system) washed in the acid that neutralization generates.The weight average molecular weight of the acrylate of the carbohydrate that so obtains and/or modification carbohydrate (21) is 400～200,000, be preferably 400～100,000, hydroxyl value is 0～200mgkOH/g, is preferably 5～150mgKOH/g, and is also preferred from resin standby aspect consideration.

The acrylate of dextrin and/or modification dextrin (22):

As the starch-series resin (a1) that contains unsaturated group, can use suitably to have 400～4,000 weight average molecular weight and every 1 molecule have the dextrin of 2～14 acryloyl groups and/or the acrylate (22) of modification dextrin.Need to prove, consider from the marresistance aspect of filming preferably have 400～4,000 weight average molecular weight and every 1 molecule and have 2～14 acryloyl groups.

At this, as the modification dextrin, can use suitably by at least a kind in the carboxylic acid, carboxylate and the carbonyl halide that are selected from 2～22 of carbon numbers a part of hydroxyl in dextrin is carried out the modification dextrin that carboxylic esterification forms.for the manufacturing of the acrylate (22) of above-mentioned dextrin and/or modification dextrin, dextrin and/or modification dextrin are mixed in following organic solvent with acrylic acid or acrylate, suitably add alkali compounds, under agitation, at approximately 60 ℃～100 ℃, more preferably make it carry out esterification or ester exchange reaction 30 minutes～10 hours at the temperature of 70～90 ℃, more preferably about 1～5 hour, can obtain the acrylate (22) of dextrin and/or modification dextrin, wherein, the use level of described dextrin and/or modification dextrin and acrylic acid or acrylate is, after dextrin and/or modification dextrin are dissolved in solvent, take the total solid composition quality of dextrin and/or modification dextrin and acrylic acid or acrylate (for example methyl acrylate) as benchmark, dextrin and/or modification dextrin are 50～99 quality %, the scope of preferred 60～98 quality %, acrylic acid or acrylate are 1～50 quality %, the scope of preferred 2～40 quality, described organic solvent is for example: toluene, dimethylbenzene, cyclohexane, the hydrocarbon system solvents such as n-hexane, the ketone series solvents such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl amyl ketone, or the mixture of these solvents etc.

The acrylate of dextrin and/or modification dextrin (22) also can obtain by the following method, that is, after dextrin and/or modification dextrin are dissolved in organic solvent, add acryloyl halide (for example acryloyl chloride), (desalination acid system) washed in the acid that neutralization generates.

For the acrylate (22) of dextrin and/or modification dextrin, any of carboxylic acid that also can be by 2～22 of carbon numbers, carboxylate, carbonyl halide comes the part of its hydroxyl of carboxylic esterification.The weight average molecular weight of the acrylate of dextrin and/or modification dextrin (22) is 400～4,000, is preferably 600～3,000, and hydroxyl value is 0～200mgKOH/g, be preferably 5～150mgKOH/g, considers also preferred from resin manufacture, marresistance aspect.

Need to prove, the acryloyl radix of every 1 molecule of the acrylate (22) of dextrin and/or modification dextrin is 2～14, preferred 3～12 scope, and the reactivity during from irradiation and the tack aspect consideration of filming are preferred.As the mixing ratio of the acrylate (22) of dextrin and/or modification dextrin, be in the scope of 1～200 mass parts, preferred 5～180 mass parts with respect to photocurable compound (a3) 100 mass parts.

The starch-series resin (a1) that contains unsaturated group, by with photocurable compound described later (a3) and use, can obtain further excellent multilayer film of hardness of film.

Photoepolymerizationinitiater initiater (a2)

Photoepolymerizationinitiater initiater (a2) is the compound that the free-radical polymerised unsaturated group that the starch-series resin (a1) that contains unsaturated group and photocurable compound (a3) are had carries out radical polymerization, photo-curable coating (A) is solidified.concrete example as Photoepolymerizationinitiater initiater (a2), for example can enumerate: benzoin, benzoin methylether, benzoin ethyl ether, the benzoin isobutyl ether, diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, benzyl dimethyl ketal, 1-hydroxy-cyclohexyl-phenyl ketone, 2-methyl-2-morpholino (4-methyl mercapto phenyl)-1-propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2, 4, 6-trimethylbenzoyl phenyl phosphine oxide, 2, 4, 6-trimethylbenzoyl phenyl ethoxy phosphine oxide, benzophenone, methyl o-benzoylbenzoate, dihydroxy benaophenonel, ITX, 2, 4-dimethyl thioxanthones, 2, the 4-diethyl thioxanthone, 2, 4-two clopenthixal ketones, 2, 4, 6-three (trichloromethyl)-S-triazine, 2-methyl-4, two (the trichlorine)-S-triazines of 6-, 2-(4-methoxyphenyl)-4, two (the trichloromethyl)-S-triazines of 6-etc.These Photoepolymerizationinitiater initiaters (a2) can use separately or be used in combination more than 2 kinds.When the starch-series resin (a1) that contains unsaturated group was 100 mass parts, the content of this Photoepolymerizationinitiater initiater (a2) was in the scope of 0.1～10 mass parts, preferred 0.2～5 mass parts.

In order to promote photopolymerization reaction, Photoepolymerizationinitiater initiater (a2) also may be used photosensitive accelerant.As can and the photosensitive accelerant of use, for example can enumerate: triethylamine, triethanolamine, methyl diethanolamine, 4-dimethylaminobenzoic acid methyl esters, EDMAB, 4-dimethylaminobenzoic acid isopentyl ester, benzoic acid (2-dimethylamino) ethyl ester, michaelis ketone, 4, the tertiary amines such as 4 '-diethylamino benzophenone are; The alkylphosphines such as triphenylphosphine system; The thioether such as β-Thiodiglycol system etc.When the starch-series resin (a1) that contains unsaturated group was 100 mass parts, these photosensitive accelerants were preferably the scope of 0.1～5 mass parts.

Photocurable compound (a3):

Photocurable compound (a3) be preferably choosing freely free-radical polymerised unsaturated monomer, contain the resin of free-radical polymerised unsaturated group and contain free-radical polymerised unsaturated group and group that the resin of thermosetting functional group forms at least a kind of compound and/or resin.Free-radical polymerised unsaturated monomer can be enumerated 2 officials' energy polymerizable monomers, above polymerizable monomer, 1 official of 3 officials' energy can polymerizable monomer.

as 2 officials' energy polymerizable monomers, for example can enumerate: ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, propane diols two (methyl) acrylate, DPG two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1, 4-butanediol two (methyl) acrylate, 1, 6-hexylene glycol two (methyl) acrylate, bisphenol-A epoxy ethane modification two (methyl) acrylate, bisphenol-A epoxy propane modification two (methyl) acrylate, 2-hydroxyl 1-acryloxy-3-methacryloxy propane, tristane dimethanol two (methyl) acrylate, phosphoric acid hydrogen two ((methyl) acrylyl oxy-ethyl) ester (ジ (メタ) ア Network リロイ Le オキシエチ Le アシ Star De Off オス Off エ one ト) etc.In addition, as 2 officials' energy polymerizable monomers, can also use with trade names such as " カヤラ Star De HX-220 ", " カヤラ Star De 620 ", " カヤラ Star De R-604 ", " MANDA " above by the commercially available monomer of Japanese chemical drug (strain).

At this, (methyl) acrylate refers to acrylate and/or methacrylate.

as the 3 above polymerizable monomers of officials' energy, for example can enumerate: trimethylolpropane tris (methyl) acrylate, trimethylolpropane oxirane modification three (methyl) acrylate, trimethylolpropane epoxy pronane modification three (methyl) acrylate, three (methyl) acrylic acid glyceride, oxirane modification three (methyl) acrylic acid glyceride, epoxy pronane modification three (methyl) acrylic acid glyceride, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, isocyanuric acid oxirane modification triacrylate, dipentaerythritol six (methyl) acrylate etc.

as the 1 official's energy polymerizable monomer that may be used, can enumerate: styrene, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid cyclohexene ester, 2-hydroxyl (methyl) acrylic acid, (methyl) hydroxypropyl acrylate, (methyl) acrylic acid tetrahydro furfuryl ester, 6-caprolactone modification (methyl) acrylic acid tetrahydro furfuryl ester, (methyl) acrylic acid phenoxy ethyl, (methyl) acrylic acid phenoxy group macrogol ester, (methyl) acrylic acid double cyclopentenyl ester, (methyl) acrylic acid double cyclopentenyl 2-ethoxyethyl acetate, (methyl) isobornyl acrylate, (methyl) benzyl acrylate, 6-caprolactone modification (methyl) hydroxy-ethyl acrylate, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, (methyl) acrylic acid 2-hydroxyl-3-phenoxy group propyl ester, (methyl) acrylic acid 2-hydroxyl-3-butoxy propyl ester, (methyl) acrylic acid phthalic acid list hydroxyl ethyl ester, to cumyl phenol oxirane modification (methyl) acrylate, N-methylol (methyl) acrylamide, N-methylol (methyl) acrylamide butyl ether, acryloyl morpholine, (methyl) acrylic acid dimethylamino ethyl ester, NVP etc.As free-radical polymerised unsaturated monomer, consider from aspects such as curing property, tack, marresistances, preferably use the 2 above polymerizable monomers of officials' energy.

What is called contains the resin of free-radical polymerised unsaturated group, to have the resin of free-radical polymerised unsaturated group more than 2 in 1 molecule, for example can enumerate: unsaturated acrylic resin, unsaturated urethane resin, unsatured epoxy resin, polyester (methyl) acrylate, unsaturated organosilicon resin, urethane acrylate, epoxy acrylate, polyester acrylate etc. can use to be selected from one kind or two or more in these resins.

The above-mentioned resin that contains free-radical polymerised unsaturated group and thermosetting functional group is to have free-radical polymerised unsaturated group and each resin more than 1 of thermosetting functional group in 1 molecule.Consider preferably have a plurality of these unsaturated groups and this functional group from the viewpoint of the curing of filming.As thermosetting functional group, can use the functional groups such as hydroxyl, acidic group, epoxy radicals, NCO.As this acidic group, can enumerate carboxyl, phosphate etc.

As the above-mentioned concrete example that contains the resin of free-radical polymerised unsaturated group and thermosetting functional group, can enumerate such as: contain free-radical polymerised unsaturated group and epoxy radicals acrylic resin, contain free-radical polymerised unsaturated group and NCO acrylic resin, contain free-radical polymerised unsaturated group mylar, contain free-radical polymerised unsaturated group and contain cresols phenolic resin varnish type epoxy resin of epoxy radicals etc.

In addition, in the situation that photocurable compound (a3) has thermosetting functional group, may be used such as: amino resins, polyisocyanate compound, contain epoxy compounds etc.As above-mentioned amino resins, can use such as melmac, guanamine resin, carbamide resin etc.

[photo-curable coating (B)]

The photo-curable coating (B) that is used for method of forming layered coating film of the present invention is the coating that contains photocurable compound and/or light-cured resin (b1), Photoepolymerizationinitiater initiater (b2) and starch-series resin (b3).

Photocurable compound and/or light-cured resin (b1):

Photocurable compound and/or light-cured resin (b1) can use the material identical with above-mentioned photocurable compound (a3).

In addition, in the situation that photocurable compound and/or light-cured resin (b1) have thermosetting functional group, may be used such as amino resins, polyisocyanate compound, contain epoxy compounds etc.As above-mentioned amino resins, can use such as melmac, guanamine resin, carbamide resin etc.

Photoepolymerizationinitiater initiater (b2)

Photoepolymerizationinitiater initiater (b2) is the compound that the free-radical polymerised unsaturated group that photocurable compound and/or light-cured resin (b1) are had carries out radical polymerization, photo-curable coating (B) is solidified.As the concrete example of Photoepolymerizationinitiater initiater (b2), can enumerate for example identical with Photoepolymerizationinitiater initiater (a2) material.These Photoepolymerizationinitiater initiaters (b2) can use separately or be used in combination more than 2 kinds.When photocurable compound and/or light-cured resin (b1) were 100 mass parts, the content of Photoepolymerizationinitiater initiater (b2) was in the scope of 0.1～10 mass parts, preferred 0.2～5 mass parts.

In order to promote photopolymerization reaction, Photoepolymerizationinitiater initiater (b2) also may be used photosensitive accelerant.As the photosensitive accelerant that may be used, for example can enumerate in Photoepolymerizationinitiater initiater (a2) and the identical material of photosensitive accelerant of use.When photocurable compound and/or light-cured resin (b1) were 100 mass parts, these photosensitive accelerants were preferably the scope of 0.1～5 mass parts.

Starch-series resin (b3):

The starch-series resin (b3) that is used for photo-curable coating (B) does not comprise unsaturated group in principle.As starch-series resin (b3), preferred use is selected from least a kind in starch-series resin described later (1), starch-series resin (2) and starch-series resin (3).As the mixing ratio of above-mentioned starch-series resin (b3), with respect to photocurable compound and/or light-cured resin (b1) 100 mass parts, be in the scope of 1～200 mass parts, preferred 5～180 mass parts.

Starch-series resin (1)

Starch-series resin (1) is to make modified starch (b30) and the resin that has product (I) reaction of NCO and obtain described later.

Modified starch (b30)

Modified starch (b30) can use the material identical with above-mentioned modified starch (a10).

Product (I) with NCO

Product (I) with NCO can make polyisocyanate compound (b31) and polyalcohol (b32) react and obtain.

for polyisocyanate compound (b31), for example can enumerate: IPDI, toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, the tolidine vulcabond, naphthalene diisocyanate, triphenylmethane triisocyanate, the tri o cresyl thiophosphate phenyl isocyanate, phenylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, LDI, the xyxylene vulcabond, two (isocyanato-methyl) cyclohexane, two (isocyanato-) hexahydrotoluene, dicyclohexyl methyl hydride diisocyanate, isopropylidene two (cyclohexyl isocyanate), 3-(2 '-isocyanato-cyclohexyl) propyl group isocyanates, dianisidine diisocyanate, diphenyl ether vulcabond etc.Wherein, from hardness, tack, resistance to impact aspect consideration, preferably use IPDI, hexamethylene diisocyanate.

As the example of the commercially available product of polyisocyanate compound (b31), can enumerate " バ one ノ Star Network D-750 ,-800, DN-950 ,-970 or 15-455 " (above be large Japanese ink chemical industry (strain) goods); " デスモジユ one Le L, N, HL or N 3390 " (Germany, バイエ Le society goods), " タケネ one ト D-102, タケネ one ト D-170HN, タケネ one ト D-202, タケネ one ト D-110 or タケネ one ト D-123N " (military field pharmaceutical industries (strain) goods); " コロネ one ト EH, L, HL or 203 " (Japanese Port リウレタ Application industry (strain) goods) or " DURANATE 24A-90CX " (Asahi Chemical Industry's industry (strain) goods) etc.

As above-mentioned polyalcohol (b32), specifically can enumerate: aklylene glycol, the alkylidene polyol more than 3 yuan, ethoxylated polyhydric alcohol and PEPA, acrylic polyol and other polyalcohol.

As aklylene glycol, for example can enumerate: ethylene glycol, propane diols, 1,3-BDO, BDO, 1,5-PD, 1, the glycols such as 6-hexylene glycol, neopentyl glycol, cyclohexane-Isosorbide-5-Nitrae-dihydroxymethyl, methyl pentanediol, hydrogenated bisphenol A.

As the alkylidene polyol more than 3 yuan, can enumerate such as ternary alcohols such as glycerine, trimethylolethane, trimethylolpropanes; The alkylidene polyol classes more than 4 yuan such as pentaerythrite, Alpha-Methyl glucosides, D-sorbite.

As ethoxylated polyhydric alcohol, can enumerate the ヘキソ one Le class of the polyethylene glycol made such as the opening that utilizes oxyalkylene (being specially oxirane, diethylene glycol, expoxy propane, DPG, epoxy butane, oxolane etc.), polypropylene glycol, polytetramethylene glycol, triethylene glycol, poly-(oxygen ethene/oxypropylene) glycol, polymer with bis phenol A glycol ether, polymer with bis phenol A propylene glycol, sucrose, dipentaerythritol etc. etc.

As PEPA, can enumerate the material that for example utilizes organic dicarboxylic acid or its acid anhydrides and the organic diol composition polycondensation reaction gained under the condition of organic diol surplus.Particularly, can enumerate PEPA as the condensation product of condensation product, adipic acid and the neopentyl glycol of adipic acid and ethylene glycol.

As organic dicarboxylic acid used herein, can enumerate carbon number and be 2～44, particularly 4～36 fatty family, ester ring type or fragrant family dicarboxylic acids, for example, butanedioic acid, adipic acid, azelaic acid, decanedioic acid, maleic acid, fumaric acid, glutaric acid, chlordene heptane dicarboxylic acids, cyclohexane dicarboxylic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), tetrahydrophthalic acid, tetrachlorophthalic acid etc.In addition, except these dicarboxylic acids, can on a small quantity and use the acid anhydrides of the polybasic carboxylic acid with 3 above carboxyls, the addition product of unrighted acid etc.In addition, as the organic diol composition, for example can enumerate: ethylene glycol, propane diols, butanediol, BDO, 1, the aklylene glycols such as 6-hexylene glycol, neopentyl glycol; Hydroxymethyl-cyclohexane, butyl ethyl amyl group glycol, methyl pentanediol etc., these organic diols according to circumstances also can on a small quantity and be used the polyalcohols more than 3 yuan such as trimethylolpropane, glycerine, pentaerythrite.

In polyalcohol (b32), for resistance to impact and resistance to bend(ing), select free ethylene glycol, propane diols, 1,4-butanediol, 1, the polyalcohol in the group that 6-hexylene glycol, diethylene glycol, triethylene glycol, hydrogenated bisphenol A, glycerine, trimethylolethane, trimethylolpropane, pentaerythrite, dipentaerythritol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly-(oxygen ethene/oxypropylene) glycol, bisphenol-A glycol ether, polymer with bis phenol A propylene glycol form is specially suitable.

The reaction of polyisocyanate compound (b31) and polyalcohol (b32) is preferably at organic solvent (hydrocarbon systems such as toluene, dimethylbenzene, cyclohexane, n-hexane; The esters such as methyl acetate, ethyl acetate, butyl acetate system; The ketone such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl amyl ketone system; Or the mixture of these solvents etc.) carry out in.reaction ratio as polyisocyanate compound (b31) and polyalcohol (b32), according to being NCO base/OH base=1/0.4～1/0.95 based on the molal quantity of the OH base of polyalcohol (b32) with respect to the molal quantity based on the NCO base of polyisocyanate compound (b31), preferred 1/0.5～1/0.9, mix polyisocyanate compound (b31) and polyalcohol (b32), so that free isocyanates is residual, suitably add for example Mono-n-butyltin, the catalyst such as Dibutyltin oxide, under agitation, at approximately 50 ℃～approximately 200 ℃, at the temperature of preferred 60～150 ℃ of left and right, make its reaction 30 minutes～10 hours, preferred about 1～5 hour, can prepare thus product (I) solution with NCO.Nco value as the product with NCO (I) that obtains is preferably 5～250mgNCO/g, is particularly preferably the scope of 7～200mgNCO/g.

At this, can suitably regulate modified starch (b30) and have the mixing ratio of the product (I) of NCO according to desired film performance.preferably obtain by the following method: starch and/or modified starch (b30) are mixed in following organic solvent with the product with NCO (I), suitably add Mono-n-butyltin, the catalyst such as Dibutyltin oxide, under agitation, at approximately 50 ℃～200 ℃, more preferably make it carry out addition reaction 30 minutes～10 hours at the temperature of 60～150 ℃, more preferably about 1～5 hour, can obtain starch-series resin (1), wherein, described starch and/or modified starch (b30) with the use level with product (I) of NCO are, take the total solid composition quality of starch and/or modified starch (b30) and the product (I) with NCO as benchmark, modified starch is 50～99 quality %, the scope of preferred 60～98 quality %, product (I) with NCO is 1～50 quality %, the scope of preferred 2～40 quality %, described organic solvent for example comprises: toluene, dimethylbenzene, cyclohexane, the hydrocarbon system solvents such as n-hexane, the ketone series solvents such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl amyl ketone, or the mixture of these solvents etc.

At this, in order to obtain filming of finishability, pencil hardness, marresistance, tack, alkali resistance and solvent resistance equilibrium, also preferred modified starch (b30) and have NCO product (I) mixing ratio in the above range.

The number-average molecular weight of the starch-series resin (1) that obtains is preferably 3,000～200,000 scope.Can or be dispersed in the organic solvent series solvent the dissolving of the resin combination so made, use suitably as the binding agent of starch-series coating.

Starch-series resin (2)

Starch-series resin (2) is to make modified starch (b30), have the product (I) of NCO and vinyl copolymer resin (b33) reaction and the resin that obtains.

Modified resin (b30) and have the product (I) of NCO is as described in the explanation in " starch-series resin (1) ".Vinyl copolymer resin (b33) can make the mixture of free-radical polymerised unsaturated monomer carry out Raolical polymerizable under the existence of organic solvent and polymerization initiator and obtain.

Mixture as above-mentioned free-radical polymerised unsaturated monomer, for the multilayer film that forms finishability, tack, marresistance, solvent resistance and have excellent weather resistance, the mixture of preferred this free-radical polymerised unsaturated monomer comprises: with respect to the gross mass of this mixture, the free-radical polymerised unsaturated monomer of aromatic series is 1～90 quality %, be preferably 5～80 quality %, 10～85 quality % more preferably; The free-radical polymerised unsaturated monomer of hydroxyl is 1～50 quality %, be preferably 2～40 quality %, 5～30 quality % more preferably; Other free-radical polymerised unsaturated monomer is 0～98 quality %, be preferably 2～95 quality %, 5～90 quality % more preferably.

As the free-radical polymerised unsaturated monomer of fragrant family, can enumerate such as styrene, vinyltoluene, 2-methyl styrene, t-butyl styrene, chlorostyrene, vinyl naphthalene etc.

as the free-radical polymerised unsaturated monomer of hydroxyl, can enumerate: acrylic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, the acrylic acid hydroxy propyl ester, methacrylic acid hydroxyl propyl ester, acrylic acid 4-hydroxyl butyl ester, methacrylic acid 4-hydroxyl butyl ester, methacrylic acid 2-hydroxy propyl ester, the carbon number of the alkyl such as methacrylic acid 3-hydroxy propyl ester is the hydroxyalkyl acrylate of 2～8 acrylic or methacrylic acid, (ダイセ Le KCC makes (methyl) acrylic acid hydroxyalkyl acrylate lactone modifier, trade name " プラ Network セ Le F " series) etc.Wherein, consider with the viewpoint of guaranteeing paint stability from improving with modified starch (b30), compatibility with product (I) of NCO, particularly preferably contain at least a kind that is selected from acrylic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, acrylic acid hydroxy propyl ester, methacrylic acid hydroxyl propyl ester and acrylic acid 4-hydroxyl butyl ester.

as other free-radical polymerised unsaturated monomers, can enumerate: (methyl) acrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid etc. contain carboxyl polymerism unsaturated monomer, for example: methyl acrylate, ethyl acrylate, the acrylic acid n-propyl, isopropyl acrylate, acrylic acid just, the XOR tert-butyl ester, Hexyl 2-propenoate, 2-EHA, the acrylic acid n-octyl, decyl acrylate, lauryl acrylate, cyclohexyl acrylate, methyl methacrylate, EMA, n propyl methacrylate, isopropyl methacrylate, methacrylic acid just, the XOR tert-butyl ester, hexyl methacrylate, 2-Propenoic acid, 2-methyl-, octyl ester, decyl-octyl methacrylate, lauryl methacrylate, Arrcostab or the cycloalkyl ester of the carbon number 1～18 of the acrylic acid such as cyclohexyl methacrylate or methacrylic acid, the N-substituted acrylamides such as N hydroxymethyl acrylamide, N-butoxymethyl acrylamide, N-methoxy acrylamide, N-methylol methacrylamide, N-butoxymethyl Methacrylamide system or N-substituent methyl acrylamide monomer, in addition, these polymerism unsaturated monomers also can comprise fatty acid modified polymerism unsaturated monomer.

Comprise the polymerism unsaturated monomer that has the polymerism unsaturated group from the end of the hydrocarbon chain of aliphatic acid in fatty acid modified polymerism unsaturated monomer.As fatty acid modified polymerism unsaturated monomer, for example can enumerate by making aliphatic acid and the monomer that contains the reaction of epoxy-based polymerization unsaturated monomer and/or hydroxyl polymerism unsaturated monomer and obtain.

as aliphatic acid, can enumerate drying oil fatty acid, semi-drying oil aliphatic acid and nondrying oil aliphatic acid, as drying oil fatty acid and semi-drying oil aliphatic acid, for example can enumerate: fish oil fatty acid, dehydrated castor oil fatty acid, safflower oil aliphatic acid, linseed oil aliphatic acid, soya fatty acid, the acid of sesame oil fat, poppy seed oil aliphatic acid, perilla oil aliphatic acid, hemp-seed oil aliphatic acid, grape-pip oil aliphatic acid, corn oil fatty acid, ready denier oil acid, sunflower oil aliphatic acid, cottonseed oil fatty acid, walnut oil fat acid, rubber seed oil aliphatic acid, Ha イジエ Application acid aliphatic acid etc., in addition, as nondrying oil aliphatic acid, for example can enumerate: coco-nut oil fatty acid, the hydrogenated coconut fatty acid oil, palm oil fatty acid etc.These aliphatic acid can use separately respectively or be used in combination more than 2 kinds.And then these aliphatic acid can also and be used with caproic acid, capric acid, laurate, myristic acid, palmitic acid, stearic acid etc.

As the monomer that can make itself and above-mentioned fatty acid response in order to make fatty acid modified polymerism unsaturated monomer, the polymerism unsaturated monomer that contains epoxy radicals is suitable, for example can enumerate: (methyl) glycidyl acrylate, (methyl) acrylic acid Beta-methyl ethylene oxidic ester, (methyl) acrylic acid 3,4-epoxy radicals cyclohexyl methyl esters, (methyl) acrylic acid 3,4-epoxy radicals cyclohexyl ethyl ester, (methyl) acrylic acid 3,4-epoxy radicals cyclohexyl propyl ester, allyl glycidyl ether etc.

Carry out Raolical polymerizable by the mixture that for example makes above-mentioned free-radical polymerised unsaturated monomer under the existence of polymerization initiator in organic solvent, can prepare easily vinyl copolymer resin (b33), mixture by dripping equably free-radical polymerised unsaturated monomer and the mixture of polymerization initiator, make its reaction approximately 30 minutes～6 hours, preferred 1～5 hour under the reaction temperature of for example 60～200 ℃, preferred 80～180 ℃, can obtain target product.

As above-mentioned organic solvent, can enumerate such as hydrocarbon system solvents such as toluene, dimethylbenzene, cyclohexane, n-hexanes; The ester series solvents such as methyl acetate, ethyl acetate, butyl acetate; The ketone series solvents such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl amyl ketone; Or the mixture of these solvents etc.

The hydroxyl value of preferred vinyl copolymer resin (b33) is in the scope of 5～400mgKOH/g, and weight average molecular weight is 3,000～100, and 000, particularly 5,000～20, in 000 scope.Can make the vinyl copolymer resin (b33) of making as mentioned above dissolve or be dispersed in the organic solvent series solvent uses.

Starch-series resin (2) is to make modified starch (b30), have that the product (I) of NCO and vinyl copolymer resin (b33) react and the resin that obtains.At this, the ratio of modified starch (b30), the product (I) with NCO and vinyl copolymer resin (b33) can suitably be regulated according to desired film performance.

starch-series resin (2) can obtain by the following method: with modified starch (b30), have the product (I) of NCO and vinyl copolymer resin (b33) with about the described solvent phase of manufacturing of starch-series resin (1) with organic solvent in mix, suitably add Mono-n-butyltin, the tin catalysts such as Dibutyltin oxide, under agitation, at approximately 50 ℃～approximately 200 ℃, more preferably the temperature of 60～150 ℃ of left and right makes its reaction 30 minutes～10 hours, more preferably about 1～5 hour, wherein, described modified starch (b30), having the product (I) of NCO and the use level of vinyl copolymer resin (b33) is, with modified starch (b30), having the product (I) of NCO and the total solid composition weight of vinyl copolymer resin (b33) is benchmark, modified starch (b30) is 60～99 quality %, the more preferably scope of 65～95 quality %, product (I) with NCO is 1～39 quality %, the more preferably scope of 2～33 quality %, vinyl copolymer resin (b33) is 1～39 quality %, the more preferably scope of 2～33 quality %.

In order to obtain filming of finishability, pencil hardness, marresistance, tack, alkali resistance and solvent resistance equilibrium, also the mixing ratio of preferred modified starch (b30), the product (I) with NCO and vinyl copolymer resin (b33) is in above-mentioned scope.

Need to prove, the number-average molecular weight of starch-series resin (2) is preferably 3,000～200,000 scope.Can make the starch-series resin (2) for preparing as mentioned above dissolve or be dispersed in the organic solvent series solvent uses suitably.

Starch-series resin (3)

Starch-series resin (3) is the resin that contains the product (II) that vinyl copolymer resin (b33) is bonded in form on modified starch (b30) by glycerol polymerization.And then, also can use product (II) and the aforementioned resin that has product (I) reaction of NCO and obtain, described product (I) with NCO makes polyisocyanate compound (b31) and polyalcohol (b32) react and obtain.Modified starch (b30) is as described in the explanation in " starch-series resin (1) ".

At present, disclose in No. 3425971 specification of United States Patent (USP) and No. 3981100 specification of United States Patent (USP) and use cerium salt to cause the glycerol polymerization of the vinyl monomer of catalyst as radical polymerization in the starch of aqueous dispersion or pulpous state or modified starch.In addition, disclose styrene and acrylic monomer in JP 54-120698 communique to the glycerol polymerization of starch as the maleic acid modification of the compound that contains unsaturated group.Disclose (vinyl) esterification starch in organic solvent and the glycerol polymerization of vinyl monomer in No. 8-239402, Unexamined Patent newspaper.In addition, disclose ethene base system monomer in using the solution of radical initiator to the glycerol polymerization of cellulose acetate-butyrate in JP 55-133472 communique.If replace the NC Nitroncellulose acetic acid esters with starch and/or modified starch, make the polyvinyl glycerol polymerization upper easy at starch and/or modified starch (b30).

Above, about the glycerol polymerization of polyvinyl, narrated several known cases, can be by these known method preparations as the starch-series resin (3) of target.At this, vinyl copolymer resin (b33) is to make free-radical polymerised unsaturated monomer or its mixture carry out Raolical polymerizable under the existence of organic solvent and polymerization initiator and the resin that obtains.

At this, ratio to modified starch (b30) and vinyl copolymer resin (b33) is not particularly limited, but consider from the viewpoint of filming that forms finishability, tack, marresistance, solvent resistance and have excellent weather resistance, the mixture of the monomer that preferred character of use is different is as free-radical polymerised unsaturated monomer.

Free-radical polymerised unsaturated monomer is preferably the mixture of the free-radical polymerised unsaturated monomer of following composition, consisting of of described mixture: with respect to the gross mass of described mixture, the free-radical polymerised unsaturated monomer of fragrant family is 1～90 quality %, be preferably 5～80 quality %; The free-radical polymerised unsaturated monomer of hydroxyl is 1～50 quality %, be preferably 2～40 quality %; Other free-radical polymerised unsaturated monomer is 0～98 quality %, be preferably 47～95 quality %.Need to prove, the free-radical polymerised unsaturated monomer of fragrance family, free-radical polymerised unsaturated monomer 1～50 quality % of hydroxyl and other free-radical polymerised unsaturated monomer are identical with the free-radical polymerised unsaturated monomer of enumerating in starch-series resin (2).

The glycerol polymerization of these free-radical polymerised unsaturated monomers, can carry out easily by the following method, for example, mixture and the polymerization initiator of above-mentioned free-radical polymerised unsaturated monomer is added drop-wise in the organic solvent solution that contains modified starch, makes it carry out Raolical polymerizable.Evenly drip the mixture of free-radical polymerised unsaturated monomer and the mixture of polymerization initiator, make its reaction approximately 30 minutes～6 hours, preferred 1～5 hour under the reaction temperature of for example 60～200 ℃, preferred 80～180 ℃, can obtain thus.

At this, as polymerization initiator, can use known radical initiator, but in the situation that use the method that makes its glycerol polymerization during monomer mixture and polymerization initiator are added drop-wise to the organic solvent of modified starch, preferably use the initator of peroxidating system.As the example of the initator of such peroxidating system, can enumerate: TBHP, to hydroperoxide kinds such as terpane hydrogen peroxide, cumene hydroperoxide, diisopropyl benzene hydrogen peroxide; The peroxidating laurate tert-butyl ester, peroxidized t-butyl perbenzoate, the peroxyesters such as the peroxidating capric acid tert-butyl ester; 1,5-di-tert-butyl peroxide-3,3, the ketal peroxide classes such as 5-trimethyl-cyclohexane: the ketone peroxide classes such as ethyl acetoacetate peroxide; The diacyl peroxide classes such as benzoyl peroxide.

Above-mentioned product (I) with NCO is as illustrated in " starch-series resin (1) " item.

Starch-series resin (3) can obtain by the following method: take product (II) and the total solid composition quality of product (I) with NCO as benchmark, use the product with NCO (I) of scope of product (II), 1～50 quality %, preferred 2～40 quality % of the scope of 50～99 quality %, preferred 60～98 quality %, at organic solvent (such as hydrocarbon system solvents such as toluene, dimethylbenzene, cyclohexane, n-hexanes; The ester series solvents such as methyl acetate, ethyl acetate, butyl acetate; The ketone series solvents such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl amyl ketone; Or the mixture of these solvents etc.) the middle mixing, suitably add the catalyst such as Mono-n-butyltin, Dibutyltin oxide, under agitation, make it carry out addition reaction 30 minutes～10 hours, preferred 1～5 hour at the temperature of approximately 50 ℃～approximately 200 ℃, preferred 60～150 ℃.

In order to obtain filming of finishability, pencil hardness, marresistance, tack, alkali resistance and solvent resistance equilibrium, preferably having the product (I) of NCO and the mixing ratio of product (II) is in above-mentioned scope.

Need to prove, consider from making the viewpoint such as film, preferred starch is the number-average molecular weight that resin (3) has 3,000～2,000,000 scope, particularly 3,000～200,000 scope.

Need to prove, starch-series resin (1), starch-series resin (2) and starch-series resin (3) also can be used in combination more than 2 kinds.

In photo-curable coating (A) or photo-curable coating (B), can identify by the degree of filming of utilizing the starch-series colored base as substrate, can use as required crosslinking agent, extinction material, surface configuration adjusting material, surface energy conditioning agent, hardness regulator, ultra-violet absorber, light stabilizer, defoamer, toner, natural colouring matter and the inorganic pigments etc. such as polyisocyanate compound.Need to prove, consider the crosslinking agents such as preferred polyisocyanate compound from the viewpoint that improves hardness of film.

As above-mentioned toner, can enumerate the toner of Health and human services department the 37th command defined.for example can enumerate: red No. 202 (lithol rubine BCA), red No. 203 (lake red C), red No. 204 (lake red C BA), red No. 205 (lithol red), red No. 206 (lithol red CA), red No. 207 (lithol red BA), red No. 208 (lithol red SR), red No. 219 (bright lake red R), red No. 220 (dark maroon), red No. 221 (toluidine red), red No. 228 (permanent red), orange No. 203 (permanent oranges), orange No. 204 (Benzidine orange Gs), yellow 205 (the yellow G of benzidine), red No. 404 (bright fast scarlet), red No. 405 (permanent red F5R), orange No. 401 (Chinese spreads orange), yellow No. 401 (hansa yellow), blue No. 404 (phthalocyanine blues) etc.

As natural colouring matter, particularly, class trailing plants ト prime system recklessly can be enumerated: Hu trailing plants ト element, Hu trailing plants ト alcohol, capsorubin, lycopene, annatto, crocin, canthaxanthin, annatto etc.; Flavonoids system can enumerate: the anthocyan of purple perilla element, trailing plants ト element, anthocyanin etc. and so on; The chalcone of safrole Huang, safflower etc. and so on; The flavonols of rutin sophorin, Quercetin etc. and so on; The flavonoids of cocoa pigment and so on etc.; Flavine system can enumerate riboflavin etc.; Quinone system can enumerate: the Anthraquinones of laccaic acid, carminic acid (dried female insect), the acid of purple worm, alizarin etc. and so on; Alkannin, Asian puccoon are red, the naphthoquinones class of echinochrome etc. and so on etc.; Chonglou saponin system can enumerate: chlorophyll, hemochrome etc.; Diketone system can enumerate curcumin (root tuber of aromatic turmeric root powder) etc.; The betacyanin prime system can be enumerated: beet red glycosides etc.

As inorganic pigment, can enumerate: silicic acid anhydride, magnesium silicate, talcum, kaolin, bentonite, mica, mica titanium, bismuthyl chloride, zirconia, magnesia, zinc oxide, titanium oxide, precipitated calcium carbonate, powdered whiting, light magnesium carbonate, heavy magnesium carbonate, barium sulfate, iron oxide yellow, iron oxide red, iron oxide black, ultramarine, chromium oxide, chromium hydroxide, carbon black, smithsonite etc.

The mixing ratio of organic pigment, natural colouring matter and inorganic pigment can change according to the purposes of using, desired performance.

[starch-series colored base]

The starch-series colored base as the basalis of photo-curable coating (A) or photo-curable coating (B) and be coated, is given multilayer film with design on coated article.

Starch-series resinous principle as the starch-series colored base so long as contain the resin of starch, just is not particularly limited, and preferably uses at least a in above-mentioned starch-series resin (1), starch-series resin (2) and starch-series resin (3).

Wherein, as organic solvent type coating, can use separately or be used in combination more than 2 kinds hydrocarbon system organic solvents such as toluene, dimethylbenzene, cyclohexane, n-hexane, the esters such as methyl acetate, ethyl acetate, butyl acetate are organic solvent, the ketone such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl amyl ketone are that organic solvent is as reaction dissolvent, retarder thinner, make above-mentioned starch-series resinous principle dissolving or disperse, being used for the starch-series colored base.

In addition, in the starch-series colored base, as required, also can coordinate other from the resin of natural goods.As the example from the resin of natural goods beyond starch-series, can enumerate: the polyhydroxycarboxyliacid acid of vegetative fiber (celluosic resin), PLA representative, polycaprolactam, modified polyvinylalcohol etc.

In the present invention, as the resin from natural goods, can use the resin that dissolves in solvent, wherein, preferably from cellulosic resin.

The present application people's discovery, in the present invention, by a small amount of interpolation NC Nitroncellulose and/or cellulose acetate-butyrate, the drying property of filming when using as a liquid type japanning coating becomes well, and case hardness improves.

Also can find out in addition, polyhydroxycarboxyliacid acid, particularly PLA also are improved the effect of case hardness, but the tendency of filming and becoming fragile, and be good from the balance of the film performance of cellulosic resin, is easy to use.

as can use suitably NC Nitroncellulose in the starch-series colored base, can enumerate: industrial nitrocotton BNC-HIG-2 (trade name, France ベ Le ジユラ Star Network NC society system), industrial nitrocotton RS1-4 (trade name, Korea S CNC company system), スワ Application セ Le HM1-4 (trade name, bright foreign firm of association of Co., Ltd. system), セ Le ノバ BTH1-4 (trade name, Asahi Chemical Corp's system) etc., as cellulose acetate-butyrate, can enumerate: CAB 381-0.1, CAB 381-0.5, CAB381-2, CAB531-1, CAB551-0.01, CAB551-0.2 (is all trade name, her イ one ストマ Application ケミカ Le プロダ Network Star society system) etc.

Consider from the drying property of guaranteeing the starch-series colored base, marresistance and solvent resistance aspect, preferably these from the use level of the resin of natural goods with respect to solid constituent 100 mass parts of starch-series resinous principle be below 50 mass parts, preferred 5～40 mass parts, further preferred 10～35 mass parts.In addition, the starch-series colored base can be used toner, natural colouring matter and inorganic pigment as required.

As toner, natural colouring matter and inorganic pigment, can use illustrative material in photo-curable coating (A) or photo-curable coating (B).The mixing ratio of organic pigment, natural colouring matter and inorganic pigment can according to the purposes of using, the change of desired performance, be the scope of 0.001～10 mass parts, preferred 0.01～5 mass parts with respect to starch-series binding agent 100 mass parts usually.

And then, the purpose that rises to curing property, can add existing known crosslinking agent in the starch-series colored base, for example, illustrated compound etc., melmac, melamine two resins, carbamide resin etc. in above-mentioned polyisocyanate compound (b31).

In addition, can suitably add plasticizer, ultra-violet stabilizer, metal drier, rheology control agent, depression preventing agent (Ha ジキ prevents drug), anti-sagging agent, antioxidant, delustering agent, polishing agent, anticorrisive agent, curing accelerator, scratching agent, defoamer etc.

Need to prove, as the aqueous coating of starch-series colored base, can use by applications such as roller coat dress, brush painting, dipping coating, spray-coating (non-electrostatic spraying, electrostatic spraying etc.), the mobile application of curtain, serigraphy, letterpress or printing skill and technique.

[about method of forming layered coating film]

Method of forming layered coating film of the present invention is not particularly limited coated article, can use metal, plastics, timber etc.Wherein, particularly use plastics to be coated article, by forming multilayer film of the present invention, can obtain having given the plastic products of design and hardness and marresistance.As such plastics, for example can enumerate: acrylic resin, mylar, polyamide, polycarbonate resin, ABS resin, acrylic resin, polyvinyl resin.

As coating film-forming methods of the present invention, can enumerate 3 following operations.

From the coated article of above-mentioned selection,

(operation 1) application starch-series colored base is so that be 0.1～30 μ m, be preferably 0.5～10 μ m, 1～5 μ m more preferably as dry film thickness.Then, the drying of filming after application was heating 1～40 minute lower than 100 ℃, preferred 40 ℃～90 ℃.Or solidify more than 10 minutes under normal temperature (lower than 40 ℃).

(operation 2) application photo-curable coating (A) or photo-curable coating (B) are 0.1～30 μ m, preferred 1～25 μ m, further preferred 5～20 μ m as dry film thickness.

(operation 3) can obtain multilayer film by above-mentioned filming carried out irradiation.

As above-mentioned starch-series colored base and photo-curable coating (A) or photo-curable coating or coating process (B), can enumerate such as spray-coating method, electrostatic painting method, curtain coating coating process, spin coating coating process, dipping coating method etc., can form by this coating process and film, but preferred spray-coating method wherein.

In above-mentioned coating process, can be as required with an organic solvent.For the solid component concentration of photo-curable coating (A) or photo-curable coating (B), but so long as the scope of application just is not particularly limited, be preferably the scope of 10～50 quality %.Need to prove, in order to make the organic solvent volatilization in the applying coatings that remains in after spray-coating, can be 40 ℃～90 ℃ heating 1 minute～40 minutes, or solidify more than 10 minutes under normal temperature (lower than 40 ℃).

Need to prove, solidify in order to make photo-curable coating (A) or photo-curable coating (B), can use irradiation or irradiation and heating and use system.Need to prove, this irradiation and heating and with in system, can use simultaneously irradiation and heating, also can be after irradiation application of heat, perhaps also can carry out irradiation after heating.

In the present invention, so-called irradiation refers to shine radioactive ray.As this radioactivity, be not particularly limited, can use electron beam, ultraviolet ray, visible light, α line, β line, γ line etc.Preferably wavelength is that the ultraviolet scope of 150nm～450nm is suitable.Can be according to the kind of Photoepolymerizationinitiater initiater, the irradiation source of suitably selecting to have highly sensitive wavelength uses.

As the ultraviolet irradiation source, can enumerate such as high-pressure sodium lamp, ultrahigh pressure mercury lamp, xenon lamp, carbon arc lamp, metal halide lamp, sunshine etc.To the ultraviolet illuminate condition of filming, usually being suitable for the accumulative total light quantity is 100～2,000mJ/cm ², preferred 200～1,500mJ/cm ²Scope.In the situation that irradiation ultraviolet radiation, as irradiation time, be preferably about 1 second～5 minute.

Heating means are not particularly limited, can application examples such as the drying equipment such as hot-blast stove, electric furnace, infrared induction heating.Heating-up temperature is generally 35～100 ℃ of left and right, is preferably the scope of 40～90 ℃, and being particularly suitable for coated article is the situation of plastics.Be not particularly limited heat time heating time, and the scope of common 1～30 minute is suitable.In the situation that application contains photo-curable coating (A) or the photo-curable coating (B) of solvent, wish after application by heating or solidify to carry out irradiation after making solvent evaporates.

Utilize the article of antireflective coating film formation method of the present invention, can be such as using as the materials such as electric component, mobile phone, illumination, electrical equipment, semiconductor, automatic vending machine (such as coating material, adhesives, printing material, sheet material, laminate and moulding material etc.).

Embodiment

Below, enumerate embodiment and further specifically describe the present invention, but the present invention not merely is defined in these embodiment.Need to prove, unless otherwise specified, " part " reaches " % " is that " mass parts " reaches " quality % ".

[about the embodiment of multilayer film with the film layer that is formed by photo-curable coating (A)]

The Production Example of [Production Example A-1] modified starch No.A-1 (being equivalent to modified starch (a10))

25 parts of amylomaizes (hydroxyl value 500mgKOH/g) are suspended in 200 parts of dimethyl sulfoxide (DMSO)s (DMSO), and warming while stirring to 90 ℃ keeps making in 20 minutes its gelatinization in this temperature.Add 20 parts of sodium acid carbonates in this solution as catalyst, keep 90 ℃, add 17 parts of vinyl laurates, make it this thermotonus 1 hour.Then, then add 37 parts of vinyl acetates, make its reaction 1 hour at 80 ℃ equally.Thereafter, reactant liquor is injected running water, high-speed stirred is pulverized, and filters, dehydrates, and makes modified starch No.A-1.

The Production Example of [Production Example A-2] polyurethane resin solution No.A-1 (being equivalent to product (I))

In the reaction vessel of the 1L that has thermometer, thermostat, mixer, cooling tube and Dropping feeder, pack into 125 parts of toluene, 377 parts of IPDIs (being equivalent to polyisocyanate compound), mix under blanket of nitrogen, be warming up to 80 ℃.

Then, drip 123 parts of BDOs (being equivalent to polyalcohol) with 3 hours, drip finish after, 80 ℃ of lower slakings 30 minutes, make the resin solid composition and be 80% polyurethane resin solution No.A-1.Need to prove, the nco value of the resin solid composition of polyurethane resin solution No.A-1 is 55mgNCO/g.

The Production Example (being equivalent to vinyl copolymer resin) of [Production Example A-3] acrylic resin solution No.A-1

In the reaction vessel of the 1L that has thermometer, thermostat, mixer, cooling tube and Dropping feeder, 333 parts of the toluene of packing into mix under blanket of nitrogen, are warming up to 100 ℃.Then, drip following " mixture No.A-1 " solution with 4 hours, drip finish after, 100 ℃ of lower slakings 1 hour, obtain the resin solid composition and be 60% acrylic resin solution No.A-1.The hydroxyl value of the resin solid composition of the acrylic resin solution No.A-1 that obtains is 86mgKOH/g.

[mixture No.A-1]

200 parts of styrene

150 parts of methyl methacrylates

50 parts of n-butyl acrylates

100 parts of 2-hydroxyethyl methacrylates

2,25 parts of 2 '-azo, two 2-methylbutyronitriles

The Production Example of [Production Example A-4] acrylic resin solution No.A-2 (relatively Production Example is used)

In the reaction vessel of the 1L that has thermometer, thermostat, mixer, cooling tube and Dropping feeder, 333 parts of the toluene of packing into mix under blanket of nitrogen, are warming up to 100 ℃.Then, drip following " mixture No.A-2 " solution with 4 hours, drip finish after, 100 ℃ of lower slakings 1 hour, obtain the resin solid composition and be 60% acrylic resin solution No.A-2.The hydroxyl value of the resin solid composition of the acrylic resin soln No.A-2 that obtains is 86mgKOH/g.

[mixture No.A-2]

350 parts of methyl methacrylates

50 parts of n-butyl acrylates

100 parts of 2-hydroxyethyl methacrylates

2,25 parts of 2 '-azo, two 2-methylbutyronitriles

[Production Example of starch-series resin]

The Production Example of [Production Example A-5] starch-series resin solution No.A-1

In the reaction vessel of the 1L that has thermometer, thermostat, mixer, cooling tube and cooling tube, 595 parts of the butyl acetates of packing into are warming up to 50 ℃ while stirring under blanket of nitrogen.Then, keep 50 ℃, the modified starch No.A-1 that 180 parts of Production Example A-1 are obtained packs in reaction vessel, thereafter, is warming up to 100 ℃, is stirred to the modified starch No.A-1 that packs into and dissolves fully.

Then, the polyurethane resin solution No.A-1 that the 25 parts of Production Example A-2 that pack into obtain, after being stirred to evenly, add 0.02 part of dibutyl tin laurate as catalyst, reacted 6 hours at 100 ℃ while stirring under blanket of nitrogen, obtain solid constituent and be 25% starch-series resin solution No.A-1.The nco value of the resin solid composition of starch-series resin solution No.A-1 is 0.4mgNCO/g.

The Production Example of [Production Example A-6] graft product solution (colored base is used)

In the reaction vessel of the 1L that has thermometer, thermostat, mixer, cooling tube and Dropping feeder, 466 parts of the butyl acetates of packing into are warming up to 50 ℃ while stirring under blanket of nitrogen.Then, remain on 50 ℃, the modified starch No.A-1 that 160 parts of Production Example A-1 are obtained packs in reaction vessel, thereafter, is warming up to 100 ℃, is stirred to the modified starch No.A-1 that packs into and dissolves fully.Then, with " mixture No.A-3 " solution that dripped following composition in 1 hour, after drip finishing, 100 ℃ of lower slakings 1 hour, obtain the resin solid composition and be 30% graft product solution.

[mixture No.A-3]

28 parts of styrene

4 parts of methyl methacrylates

4 parts of n-BMAs

4 parts of 2-hydroxyethyl methacrylates

4 parts of パ one カ De Star Network ス CH-50L (annotating 1)

(annotate 1) パ one カ De Star Network ス CH-50L: contain diacyl peroxide 50%, chemical drug ア Network ゾ Co., Ltd. system, polymerization initiator

The Production Example of [Production Example A-7] starch-series resin solution No.A-2 (colored base is used)

In the reaction vessel of the 1L that has thermometer, thermostat, mixer, cooling tube and cooling tube, the 581.6 parts of butyl acetates of packing into, 33.4 parts of acrylic resin solution No.A-1 that Production Example A-3 obtains are warming up to 50 ℃ while stirring under blanket of nitrogen.Then, keep 50 ℃, the modified starch No.A-1 that 160 parts of Production Example A-1 are obtained packs in reaction vessel, thereafter, is warming up to 100 ℃, is stirred to the modified starch No.A-1 that packs into and dissolves fully.

Then, the polyurethane resin solution No.A-1 that the 25 parts of Production Example A-2 that pack into obtain, after being stirred to evenly, add 0.02 part of dibutyl tin laurate as catalyst, reacted 6 hours at 100 ℃ while stirring under blanket of nitrogen, obtain solid constituent and be 25% starch-series resin solution No.A-2.The nco value of the resin solid composition of starch-series resin solution No.A-2 is 0.4mgNCO/g.

The Production Example of [Production Example A-8] starch-series resin solution No.A-3 (colored base is used)

In the reaction vessel of the 1L that has thermometer, thermostat, mixer, cooling tube and Dropping feeder, 125 parts of the toluene of packing into, 292 parts of hexamethylene diisocyanates mix under blanket of nitrogen, are warming up to 80 ℃.Then, drip 208 parts of triethylene glycols with 3 hours, drip finish after, 80 ℃ of lower slakings 30 minutes, obtain the resin solid composition and be 80% polyurethane resin solution No.A-2.The nco value of this polyurethane resin is 58mgNCO/g.

Then, in another reaction vessel of the 1L that has thermometer, thermostat, mixer and cooling tube, 600 parts of the graft product solution that 41 parts of the butyl acetates of packing into, Production Example A-6 obtain are warming up to 100 ℃ while stirring under blanket of nitrogen.Then, 25 parts of polyurethane resin solution No.A-2 obtained above pack into, after being stirred to evenly, add 0.04 part of dibutyl tin laurate as catalyst, reacted 6 hours at 100 ℃ while stirring under blanket of nitrogen, then with the butyl acetate dilution, diluting for making solid constituent is 25%, obtains starch-series resin solution No.A-3.

[manufacturing of starch-series colored base]

The Production Example of [Production Example A-9] colored base No.A-1

Starch-series resin solution No.A-1,46 parts of (23 parts of solid constituents) ア Le ペ one スト FX-7640NS (annotating 2), 3 parts of (3 parts of solid constituents) Ha イコ Application Network black (annotating 3), 1.5 parts of (1.5 parts of solid constituents) サイリシア 446 (annotating 4) and 59.5 parts of methyl ethyl ketones of adding 400 parts of (100 parts of solid constituents) Production Example A-5 to obtain, fully mix with mixer, obtain solid constituent and be 25% colored base No.A-1.

(annotate 2) ア Le ペ one スト-7640NS Japan ア Le ミニウ system society system, trade name, aluminium paste.

(annotating 3) Ha イコ Application Network is black: horizontal creek changes into Co., Ltd.'s system, the solvent based coating colouring agent.

(annotating 4) サイリシア 446: シリシア KCC of Fuji system, moisture amorphous silica (delustering agent).

The Production Example of [Production Example A-10] colored base No.A-2

Add that starch-series resin solution No.A-2 that 400 parts of (100 parts of solid constituents) Production Example A-7 obtain, 46 parts of (23 parts of solid constituents) ア Le ペ one スト FX-7640NS, 3 parts of (3 parts of solid constituents) Ha イコ Application Network are black, 1.5 parts of (1.5 parts of solid constituents) サイリシア 446 and 59.5 parts of methyl ethyl ketones, fully mix with mixer, obtain solid constituent and be 25% colored base No.A-2.

The Production Example of [Production Example A-11] colored base No.A-3

In the colored base No.A-1 that Production Example A-9 obtains, add 5 parts of タケネ one ト D-170HN (annotate 5), stir, regulate solid constituent with methyl ethyl ketone, obtain solid constituent and be 25% colored base No.A-3.

(annotate 5) タケネ one ト D-170HN: military field medicine society system, trade name, the isocyanuric acid ester of hexamethylene diisocyanate.

The Production Example of [Production Example A-12] colored base No.A-4

Add that starch-series resin solution No.A-3 that 400 parts of (100 parts of solid constituents) Production Example A-8 obtain, 46 parts of (23 parts of solid constituents) ア Le ペ one スト FX-7640NS, 3 parts of (3 parts of solid constituents) Ha イコ Application Network are black, 1.5 (1.5 parts of solid constituents) サイリシア 446 and 59.5 parts of methyl ethyl ketones, fully mix with mixer, obtain solid constituent and be 25% colored base No.A-4.

The Production Example that contains the starch-series resin (20) of unsaturated group

[Production Example A-13] contains the Production Example (addition 2-acrylyl oxy-ethyl is isocyanate-based) of the starch-series resin solution No.A-1 of unsaturated group

In the reaction vessel of the 1L that has thermometer, thermostat, mixer, cooling tube and Dropping feeder, pack into the butyl acetate that dewatered 300 parts, be warming up to while stirring 50 ℃ under blanket of nitrogen, then, remain on 50 ℃, the modified starch No.A-1 that 180 parts of Production Example A-1 are obtained packs in reaction vessel, thereafter, be warming up to 110 ℃, be stirred to the modified starch No.A-1 that packs into and dissolve fully.

Pack into 20 parts of 2-acrylyl oxy-ethyl isocyanates and 0.04 part of dibutyl tin laurate, make its reaction after 3 hours at 110 ℃, the 300 parts of butyl acetates of packing into carry out cooling, obtain solid component concentration and be 25% the starch-series resin solution No.A-1 that contains unsaturated group.

[Production Example A-14] contains the Production Example (addition IPDI-Hydroxyethyl Acrylate type) of the starch-series resin solution No.A-2 of unsaturated group

In the reaction vessel of the 1L that has thermometer, thermostat, mixer, cooling tube and Dropping feeder, 300 parts of butyl acetates, 31 parts of the IPDIs of packing into and having dewatered are warming up to 110 ℃.Then, remain on 110 ℃, with 16 parts of Hydroxyethyl Acrylate of dropping in 1 hour.Make its reaction 1 hour under the state of 110 ℃ remaining on, then the modified starch No.A-1 that 180 parts of Production Example A-1 is obtained and 0.04 part of dibutyl tin laurate are packed in reaction vessel, make its reaction after 3 hours at 110 ℃, the 381 parts of butyl acetates of packing into carry out cooling, obtain solid component concentration and be 25% the starch-series resin solution No.A-2 that contains unsaturated group.

The Production Example of the acrylate of carbohydrate and/or modification carbohydrate (21)

[Production Example A-15] contains the Production Example of the starch-series resin solution No.A-3 of unsaturated group

10 portions of maltose are dissolved in the 50mL dimethyl formamide, add the 10mL triethylamine under 0 ℃.And then, drip the 4.5mL acryloyl chloride under 0 ℃, under agitation return to room temperature.Stir after 4 hours, with filter paper, reactant liquor is carried out suction strainer.Add 300mL acetone to make its precipitation, suction strainer leaching precipitation under reduced pressure makes it fully dry, obtains 8 parts of rough things.Then, after collecting fraction with refining eluent (ethyl acetate/methanol/water=7: 2: 1), the reduced pressure concentration organic solvent carries out freeze drying to residue, obtains 5 parts of white powders.Then, this white powder is diluted with butyl acetate, obtain solid component concentration and be 25% the starch-series resin solution No.A-3 that contains unsaturated group.

Measure the quantity of the acryloyl group in (annotating 6) contain unsaturated group to importing starch-series resin No.A-3 with NMR and confirm, result is in 8 hydroxyls that maltose has, and importing on 4 hydroxyls has acryloyl group.

(annotating 6) NMR measures: measure solvent and use heavy water, use the proton N MR of 200MHz.By (the δ value is that (the δ value is that the ratio of 4.7～5.5ppm) integrated value is obtained for the proton of anomer (the アノマ one) position of 5.9～6.6ppm) integrated value, glucose unit skeleton from the proton of acryloyl group.

The Production Example of the acrylate of dextrin and/or modification dextrin (22)

[Production Example A-16] contains the Production Example of the starch-series resin solution No.A-4 of unsaturated group

Having during distilling apparatus, temperature take into account the reaction vessel of mixer, pack into 506.2 parts of 80 parts, dextrin (glucose polymer of average polymerization several 3 on average has 11 hydroxyls), 100 parts of methyl iso-butyl ketone (MIBK)s, 0.16 part of methylnaphthohydroquinone, 5.9 parts of hydronium(ion) oxidation lithiums and methyl acrylates.

Then, one side is blown into nitrogen in this solution, heats on one side to be stirred to 90 ℃, methyl acrylate, methyl alcohol, methyl iso-butyl ketone (MIBK) is little by little distilled outside system remove.Along with distillation is removed, the methyl acrylate of minimizing and methyl iso-butyl ketone (MIBK) add the umber that reduces in reaction vessel.Due to the separating methanol amount of removing along with distillation, 4 officials can part hydroxyl cooling during by acroleic acid esterification.Reactant liquor is under reduced pressure concentrated, add ethyl acetate and object is carried out separatory in residue, obtain solid component concentration and be 25% the starch-series resin solution No.A-4 that contains unsaturated group.

[Production Example A-17] contains the Production Example of the starch-series resin solution No.A-5 of unsaturated group

The glucose polymer dextrin of use average polymerization several 4 replaces the dextrin (glucose polymer of average polymerization several 3) in Production Example A-16; import acryloyl group on 10 hydroxyls in average 14 hydroxyls that prolongation reaction time to dextrin has; in addition; A-16 is same with Production Example, obtains containing the starch-series resin solution No.A-5 of unsaturated group.

[Production Example A-18] contains the Production Example of the starch-series resin solution No.A-6 of unsaturated group

Import acryloyl group (with the hydroxy acrylic acid esterification of 1 official's energy part) on 1 hydroxyl in average 11 hydroxyls that Reaction time shorten to dextrin has, in addition, A-16 is same with Production Example, obtains containing the starch-series resin solution No.A-6 of unsaturated group.

[Production Example A-19] contains the Production Example of the starch-series resin solution No.A-7 of unsaturated group

Use glucose polymer dextrin (average polymerization several 5; 17 of average hydroxyls) dextrin (glucose polymer of average polymerization several 3 in replacement Production Example A-16; on average have 11 of hydroxyls); import acryloyl group (with the hydroxy acrylic acid esterification of 15 officials' energy parts) on 15 hydroxyls in average 17 hydroxyls that prolongation reaction time to glucose polymer dextrin has; in addition; A-16 is same with Production Example, obtains containing the starch-series resin solution No.A-7 of unsaturated group.

The Production Example (being equivalent to photocurable compound (a3)) of [Production Example A-20] photocurable compound solution No.A-1

having thermometer, thermostat, mixer, in the reaction vessel of reflux condenser and air device for blowing, pack into 888 parts of IPDIs, 0.7 part of 464 parts of acrylic acid 2-hydroxy methacrylates and Hydroquinone monomethylether, on one side air is blown in reaction vessel, be warming up to 80 ℃ on one side, kept 5 hours in this temperature, after confirming that the acrylic acid 2-hydroxy methacrylate that adds in fact all reacts, add 136 parts of pentaerythrites, 0.2 part of 372 parts of butyl acetates and dibutyl tin laurate, further remain on 80 ℃, confirm that IPDI carries out after complete reaction in fact cooling, obtain the resin solid composition and be 80% photocurable compound solution No.A-1.The number-average molecular weight of this resin is approximately 1,500.

[Production Example of photo-curable coating (A)]

The manufacturing of [Production Example A-21] photo-curable coating (A) No.A-1

The starch-series resin solution No.A-1 that contains unsaturated group that adds 100 parts of (solid constituent) Production Example A-13 and obtain, 6 parts of イ Le ガキユア 184 (annotating 7), 200 parts of photocurable compound solution No.A-1 that Production Example A-20 obtains, after dissolving, being diluted to solid component concentration with butyl acetate is 30%, obtains photo-curable coating (A) No.A-1.

(annotate 7) イ Le ガキユア 184: Ciba Co., Ltd system, optical free radical polymerization initiator.

The manufacturing of [Production Example A-22～A-31] photo-curable coating (A) No.A-2～No.A-11

Except the cooperation that is set as table 1, A-21 is same with Production Example, obtains photo-curable coating (A) No.A-2～No.A-11.

The manufacturing of [relatively Production Example A-1] colored base No.A-5

Add that acrylic resin solution No.A-2 that 400 parts of (100 parts of solid constituents) Production Example A-4 obtain, 46 parts of (23 parts of solid constituents) ア Le ペ one スト FX-7640NS, 3 parts of (3 parts of solid constituents) Ha イコ Application Network are black, 1.5 parts of (1.5 parts of solid constituents) サイリシア 446 and 59.5 parts of methyl ethyl ketones, fully mix with mixer, obtain solid constituent and be 25% colored base No.A-5.

The manufacturing of [relatively Production Example A-2] photo-curable coating No.A-12

In the photocurable compound solution No.A-1 that 100 parts of (solid constituent) Production Example A-20 obtain, add 3 parts of イ Le ガキユア 184, after dissolving, being diluted to solid component concentration with butyl acetate is 30%, obtains photo-curable coating No.A-12.

[about the test plate of material]

Use the 2.0mm * 100mm of サイコラ Star Network Y665C-450 (GE plastics Japan Co., Ltd system, trade name, ABS resin) * 150mm as breadboard.

[embodiment A-1]

Operation 1: with above-mentioned breadboard with the isopropyl alcohol degreasing after, the colored base No.A-1 that obtains by aerial spraying application Production Example A-9 so that dry coating is 8 μ m, makes its under 60 ℃ dry 15 minutes, formation is filmed.

Operation 2: photo-curable coating (A) No.A-1 that obtains by aerial spraying application Production Example A-21, so that dry coating is 12 μ m, make its under 60 ℃ dry 5 minutes, formation is filmed.

Operation 3: use high voltage mercury lamp radiation 600mJ/cm ²Ultraviolet ray make it carry out photocuring, form multilayer film No.A-1.

[embodiment A-2～A-15]

Except adopting the coating shown in table 2 and operation, same with embodiment A-1, form multilayer film No.A-2～No.A-15.

[Comparative examples A-1～A-3]

Except adopting the coating shown in table 3 and operation, same with embodiment A-1, form multilayer film No.A-16～No.A-18.

Table 3

Use has the breadboard of above-mentioned multilayer film No.A-1～No.A-18, supplies in test according to experimental condition described later.With the table 2 that the results are shown in of embodiment, with the table 3 that the results are shown in of comparative example.

[about the embodiment of multilayer film with the film layer that is formed by photo-curable coating (B)]

The Production Example of [Production Example B-1] modified starch No.B-1 (being equivalent to modified starch (b30))

25 parts of amylomaizes (hydroxyl value 500mgKOH/g) are suspended in 200 parts of dimethyl sulfoxide (DMSO)s (DMSO), and warming while stirring to 90 ℃ keeps making in 20 minutes its gelatinization in this temperature.Add 20 parts of sodium acid carbonates in this solution as catalyst, keep 90 ℃, add 17 parts of vinyl laurates, make it this thermotonus 1 hour.Then, then add 37 parts of vinyl acetates, make its reaction 1 hour at 80 ℃ equally.Then, reactant liquor is injected running water, high-speed stirred is pulverized, and filters, dehydrates, and makes modified starch No.B-1.

The Production Example of [Production Example B-2] polyurethane resin solution No.B-1 (being equivalent to product (I))

In the reaction vessel of the 1L that has thermometer, thermostat, mixer, cooling tube and Dropping feeder, pack into 125 parts of toluene, 377 parts of IPDIs (being equivalent to polyisocyanate compound (b31)), mix under blanket of nitrogen, be warming up to 80 ℃.Then, drip 123 parts of 1.4-butanediols (being equivalent to polyalcohol (b32)) with 3 hours, drip finish after, 80 ℃ of lower slakings 30 minutes, make the resin solid composition and be 80% polyurethane resin solution N0.B-1.Need to prove, the nco value of the resin solid composition of polyurethane resin solution No.B-1 is 55mgNCO/g.

The Production Example of [Production Example B-3] polyurethane resin solution No.B-2 (being equivalent to product (I))

In the reaction vessel of the 1L that has thermometer, thermostat, mixer, cooling tube and Dropping feeder, pack into 125 parts of toluene, 325 parts of IPDIs (being equivalent to polyisocyanate compound (b31)), mix under blanket of nitrogen, be warming up to 80 ℃.Then, drip 117 parts of triethylene glycols (being equivalent to polyalcohol (b 32)) with 3 hours, drip finish after, 80 ℃ of lower slakings 30 minutes, make the resin solid composition and be 80% polyurethane resin solution No.B-2.Need to prove, the nco value of the resin solid composition of polyurethane resin solution No.B-2 is 57mgNCO/g.

The Production Example (being equivalent to vinyl copolymer resin (b33)) of [Production Example B-4] acrylic resin solution No.B-1

In the reaction vessel of the 1L that has thermometer, thermostat, mixer, cooling tube and Dropping feeder, the 333 parts of toluene of packing into mix under blanket of nitrogen, are warming up to 100 ℃.Then, drip following " mixing No.B-1 " solution with 4 hours, drip finish after, 100 ℃ of slakings 1 hour, obtain the resin solid composition and be 60% acrylic resin solution No.B-1.Hydroxyl value in the resin solid composition of the acrylic resin solution No.B-1 that obtains is 86mgKOH/g.

[mixture No.B-1]

200 parts of styrene

150 parts of methyl methacrylates

50 parts of n-butyl acrylates

100 parts of 2-hydroxyethyl methacrylates

2,25 parts of 2 '-azo, two 2-methylbutyronitriles

The Production Example of [Production Example B-5] acrylic resin solution No.B-2 (relatively Production Example)

In the reaction vessel of the 1L that has thermometer, thermostat, mixer, cooling tube and Dropping feeder, the 333 parts of toluene of packing into mix under blanket of nitrogen, are warming up to 100 ℃.Then, drip following " mixture No.B-2 " solution with 4 hours, drip finish after, 100 ℃ of slakings 1 hour, obtain the resin solid composition and be 60% acrylic resin solution No.B-2.Hydroxyl value in the resin solid composition of the acrylic resin soln No.B-2 that obtains is 86mgKOH/g.

[mixture No.B-2]

350 parts of methyl methacrylates

50 parts of n-butyl acrylates

100 parts of 2-hydroxyethyl methacrylates

2,25 parts of 2 '-azo, two 2-methylbutyronitriles

[Production Example of starch-series resin (1) and starch-series resin (2)]

The Production Example of [Production Example B-6] starch-series resin solution No.B-1

In the reaction vessel of the 1L that has thermometer, thermostat, mixer, cooling tube and cooling tube, the 595 parts of butyl acetates of packing into are warming up to 50 ℃ while stirring under blanket of nitrogen.Then, keep 50 ℃, the modified starch No.B-1 that the 180 parts of Production Example B-1 that pack in the reaction vessel obtain is warming up to thereafter 100 ℃, is stirred to the modified starch No.B-1 that packs into and dissolves fully.

Then, the polyurethane resin solution No.B-1 that the 25 parts of Production Example B-2 that pack into obtain, after being stirred to evenly, add 0.02 part of dibutyl tin laurate as catalyst, reacted 6 hours at 100 ℃ while stirring under blanket of nitrogen, obtain solid constituent and be 25% starch-series resin solution No.B-1.The nco value of the resin solid composition of starch-series resin solution No.B-1 is 0.4mgNCO/g.

The Production Example of [Production Example B-7～B-9] starch-series resin solution No.B-2～No.B-4

Except the cooperation content that is set as table 4, B-6 is same with Production Example, obtains starch-series resin solution No.B-2～No.B-4.Characteristic also is shown in table 4 in the lump.

Table 4

Numerical value in cooperation is mass parts, expression solid constituent in ().

[Production Example of starch-series resin (3)]

The manufacturing of [Production Example B-10] graft product solution

In the reaction vessel of the 1L that has thermometer, thermostat, mixer, cooling tube and Dropping feeder, the 466 parts of butyl acetates of packing into are warming up to 50 ℃ while stirring under blanket of nitrogen.Then, remain on 50 ℃, the modified starch No.B-1 that the 160 parts of Production Example B-1 that pack in the reaction vessel obtain thereafter, is warming up to 100 ℃, is stirred to the modified starch No.B-1 that packs into and dissolves fully.Then, with " mixture No.B-3 " solution that dripped following composition in 1 hour, after drip finishing, 100 ℃ of lower slakings 1 hour, obtain the resin solid composition and be 30% graft product solution.

" mixture No.B-3 "

28 parts of styrene

4 parts of methyl methacrylates

4 parts of n-butyl acrylates

4 parts of 2-hydroxyethyl methacrylates

4 parts of パ one カ De Star Network ス CH-50L

The manufacturing of [Production Example B-11] starch-series resin solution No.B-5

In the reaction vessel of the 1L that has thermometer, thermostat, mixer, cooling tube and Dropping feeder, 125 parts of the toluene of packing into, 292 parts of hexamethylene diisocyanates mix under blanket of nitrogen, are warming up to 80 ℃.Then, drip 208 parts of triethylene glycols with 3 hours, drip finish after, 80 ℃ of lower slakings 30 minutes, obtain the resin solid composition and be 80% polyurethane resin solution.The nco value of this polyurethane resin is 58mgNCO/g.Then, in another reaction vessel of the 1L that possesses thermometer, thermostat, mixer and cooling tube, the 41 parts of butyl acetates of packing into, 600 parts of graft product solution that Production Example B-10 obtains are warming up to 100 ℃ while stirring under blanket of nitrogen.Then, the 25 parts of polyurethane resin solutions obtained above of packing into, after being stirred to evenly, add 0.04 part of dibutyl tin laurate as catalyst, under blanket of nitrogen while stirring 100 ℃ the reaction 6 hours after, with butyl acetate dilution, obtain solid constituent and be 25% starch-series resin solution No.B-5.

[manufacturing of starch-series colored base]

The manufacturing of [Production Example B-12] colored base No.B-1

Add that starch-series resin solution No.B-1 that 400 parts of (100 parts of solid constituents) Production Example B-6 obtain, 46 parts of (23 parts of solid constituents) ア Le ペ one スト FX-7640NS, 3 parts of (3 parts of solid constituents) Ha イコ Application Network are black, 1.5 parts of (1.5 parts of solid constituents) サイリシア 446 and 59.5 parts of methyl ethyl ketones, fully mix with mixer, obtain solid constituent and be 25% colored base No.B-1.

The manufacturing of [Production Example B-13] colored base No.B-2

Add that starch-series resin solution No.B-3 that 400 parts of (100 parts of solid constituents) Production Example B-8 obtain, 46 parts of (23 parts of solid constituents) ア Le ペ one スト FX-7640NS, 3 parts of (3 parts of solid constituents) Ha イコ Application Network are black, 1.5 parts of (1.5 parts of solid constituents) サイリシア 446 and 59.5 parts of methyl ethyl ketones, fully mix with mixer, obtain solid constituent and be 25% colored base No.B-2.

The manufacturing of [Production Example B-14] colored base No.B-3

In the colored base No.B-1 that Production Example B-12 obtains, add 5 parts of タケネ one ト D-170HN, stir, regulate solid constituent with methyl ethyl ketone, obtain solid constituent and be 25% colored base No.B-3.

The manufacturing of [Production Example B-15] colored base No.B-4

Add that starch-series resin solution No.B-5 that 400 parts of (100 parts of solid constituents) Production Example B-11 obtain, 46 parts of (23 parts of solid constituents) ア Le ペ one スト FX-7640NS, 3 parts of (3 parts of solid constituents) Ha イコ Application Network are black, 1.5 parts of (1.5 parts of solid constituents) サイリシア 446 and 59.5 parts of methyl ethyl ketones, fully mix with mixer, obtain solid constituent and be 25% colored base No.B-4.

The Production Example of [Production Example B-16] light-cured resin solution No.B-1

having thermometer, thermostat, mixer, in the reaction vessel of reflux condenser and air device for blowing, pack into 888 parts of IPDIs, 0.7 part of 464 parts of acrylic acid 2-hydroxy methacrylates and Hydroquinone monomethylether, be blown into air on one side in reaction vessel, be warming up to 80 ℃ on one side, kept 5 hours in this temperature, after confirming that the acrylic acid 2-hydroxy methacrylate that adds in fact all reacts, add 136 parts of pentaerythrites, 0.2 part of 372 parts of butyl acetates and dibutyl tin laurate, and then remain on 80 ℃, confirm that IPDI carries out after complete reaction in fact cooling, obtain the resin solid composition and be 80% light-cured resin solution No.B-1.The number-average molecular weight of this resin is approximately 1,500.

[Production Example of photo-curable coating (B)]

[Production Example B-17]

Add light-cured resin solution No.B-1, the starch-series resin solution No.B-1 that 184,50 parts of (solid constituent) Production Example B-6 of 3 parts of イ Le ガキユア obtain that 100 parts of (solid constituent) Production Example B-16 obtain, after dissolving, being diluted to solid component concentration with butyl acetate is 30%, obtains photo-curable coating (B) No.B-1.

[Production Example B-18～B-22]

Except the cooperation content that is set as table 5, B-17 is same with Production Example, obtains photo-curable coating No.B-2～No.B-6.

Table 5

Numeric representation solid constituent in cooperation.

The manufacturing of [relatively Production Example B-1] colored base No.B-5

Add that acrylic resin solution No.B-2 that 400 parts of (100 parts of solid constituents) Production Example B-5 obtain, 46 parts of (23 parts of solid constituents) ア Le ペ one スト FX-7640NS, 3 parts of (3 parts of solid constituents) Ha イコ Application Network are black, 1.5 parts of (1.5 parts of solid constituents) サイリシア 446 and 59.5 parts of methyl ethyl ketones, fully mix with mixer, obtain solid constituent and be 25% colored base No.B-5.

The manufacturing of [relatively Production Example B-2] photo-curable coating No.B-7

In the light-cured resin solution No.B-1 that 100 parts of (solid constituent) Production Example B-16 obtain, add 3 parts of イ Le ガキユア 184, after dissolving, being diluted to solid component concentration with butyl acetate is 30%, obtains photo-curable coating No.B-7.

[about the test plate of material]

Use 2.0mm * 100mm of サイコラ Star Network Y665C-450 (Japanese GE plastics society system, trade name, ABS resin) * 150mm as breadboard.

[Embodiment B-1]

Operation 1: with above-mentioned breadboard with the isopropyl alcohol degreasing after, the colored base No.B-1 that Production Example B-12 is obtained carries out aerial spraying, carries out application so that dry coating is 8 μ m, makes its under 60 ℃ dry 15 minutes, formation is filmed.

Operation 2: No.B-1 carries out aerial spraying to photo-curable coating (B), carries out application so that dry coating is 12 μ m, makes it 60 ℃ of dryings 5 minutes, and formation is filmed.

Operation 3: use high voltage mercury lamp radiation 600mJ/cm ²Ultraviolet ray make it carry out photocuring, form multilayer film No.B-1.

[Embodiment B-2～B-10]

Except adopting the coating shown in table 6 and operation, same with Embodiment B-1, form multilayer film No.B-2～No.B-10.

[comparative example B-1～B-3]

Except adopting the coating shown in table 7 and operation, same with Embodiment B-1, form multilayer film No.B-11～No.B-13.

Table 7

Use has the breadboard of above-mentioned multilayer film No.B-1～No.B-13, supplies in test according to following experimental condition.With the table 6 that the results are shown in of embodiment, with the table 7 that the results are shown in of comparative example.

[test method]

(annotate 8) is from the components matching of organism: about each coloring material and photo-curable coating, estimate with following benchmark.

Zero: starch-series resin or starch-series resin reaction and the resin (from the composition of organism) that obtains are engaged in coating.

*: starch-series resin or starch-series resin reaction and the resin (from the composition of organism) that obtains are not engaged in coating.

(annotating 9) finishability: with the face that the is coated with outward appearance of each multilayer film of visual valuation.

◎: good finishability

Zero: although few external waviness is arranged, finishability is good.

△: can see that at least a finishability in external waviness, loss of gloss, surface unclean (チリ flesh) descends.

*: at least a finishability during external waviness, loss of gloss, surface are unclean descends significantly.

(annotating 10) pencil hardness: based on JISK5600-5-4 (1999), for each multilayer film face with approximately 45 the degree the theta alignment pencil-leads, the degree that does not fracture with core on one side firmly is pressed on test coated plate face, with uniform speed forwards move approximately 10mm on one side.Change testing position repeatedly 5 times should operation, with the hardness mark of the hardest pencil in the not damaged situation of filming as pencil hardness.

(annotate 11) marresistance: on each multilayer film face, how commercially available business card by after being pressed in the upper reciprocating friction 20 times of filming, is judged according to degree of injury.

◎: not damage fully

Zero: almost not damage, as keep clear of observations (about 5cm) and do not see damage

△: produce slightly scratch

*: the scratch degree is serious.

(annotating 12) tack: on each multilayer film face, based on JISK5600-5-6 (1990), make the gridiron pattern of 100 1mm * 1mm on filming, Continuous pressing device for stereo-pattern on this face, after peeling rapidly, the quantity that the gridiron pattern that remains on the face of being coated with is filmed is estimated (gridiron pattern of the splitting of filming at the painted bottom coating of starch-series and photo-curable is as " peeling off " counting).

Zero: remaining number/all numbers=100/100

△: remaining number/all numbers=99～90/100

*: remaining number/all numbers=below 89/100

(annotating 13) alkali resistance: on each multilayer film face, drip 1% sodium hydrate aqueous solution 0.5mL, after placing 24 hours under the atmosphere of 20 ℃ of temperature, relative humidity 65%, clean with gauze the face of being coated with, the visual valuation outward appearance.

Zero: film coated surface is fully not abnormal

△: can see film coated surface variable color (albefaction)

*: film coated surface variable color (albefaction) is obvious

(annotating 14) solvent resistance: on each multilayer film face, place side by side 2 filter paper, drip respectively 78% ethanol and 2% formalin with suction hose on each filter paper, filter paper is wetting.Take 1 hour as the interval, carry out 5 times this utilize the dropping of glass pipette, thereafter, removed filter paper after 2 hours, remove film coated surface after filter paper by visual valuation.

Zero: do not expand fully or peel off etc. abnormal

△: the expansion that visual finding is slight or peel off etc. abnormal

*: film and dissolved

Applicability on industry

Coating film-forming methods of the present invention uses the starch-series coating from plant, and can form the multilayer film of finishability, pencil hardness, marresistance, tack, alkali resistance, solvent resistance excellence, so can be used on industry.In addition, multilayer film of the present invention uses the starch-series coating from plant, and finishability, pencil hardness, marresistance, tack, alkali resistance, solvent resistance are excellent, so be useful on industry.

Claims

1. method of forming layered coating film, it comprises:

The starch-series colored base that will contain the starch-series resin is coated with and is contained on coated article, forms the step of filming that is formed by the starch-series colored base;

Application contains the photo-curable coating (B) of photocurable compound and/or light-cured resin (b1), Photoepolymerizationinitiater initiater (b2) and starch-series resin (b3) on above-mentioned filming, and forms the step of filming that is formed by photo-curable coating (B); With

To the irradiation light of filming that is formed by photo-curable coating (B), make the step of this curing of coating,

(b3) is following for the starch-series resin, be to make modified starch (b30) and the product (I) with NCO, and vinyl copolymer resin (b33) reaction and the starch-series resin (2) that obtains, described product (I) makes polyisocyanate compound (b31) and polyalcohol (b32) react and obtain; Described vinyl copolymer resin (b33) makes the mixture that comprises other free-radical polymerised unsaturated monomer of the free-radical polymerised unsaturated monomer of hydroxyl of the free-radical polymerised unsaturated monomer of fragrant family, 1～50 quality % of 1～90 quality % and 0～98 quality % with respect to the gross mass of the mixture of free-radical polymerised unsaturated monomer carry out Raolical polymerizable and obtains; Or,

Starch-series resin (b3) is the starch-series resin (3) that comprises product (II), and described product (II) is that the mixture of other free-radical polymerised unsaturated monomer of the free-radical polymerised unsaturated monomer of hydroxyl of the free-radical polymerised unsaturated monomer of fragrant family that the gross mass of the mixture with respect to free-radical polymerised unsaturated monomer is comprised to 1～90 quality %, 1～50 quality % and 0～98 quality % carries out Raolical polymerizable and the glycerol polymerization by said mixture of the vinyl copolymer resin (b33) that obtains is bonded to modified starch (b30) and obtains.

2. multilayer film, it comprises:

The film layer that is formed by the starch-series colored base;

Make layer on above-mentioned film layer, that formed by the photo-curable coating (B) that contains photocurable compound and/or light-cured resin (b1), Photoepolymerizationinitiater initiater (b2) and starch-series resin (b3) carry out the film layer that photocuring forms

3. a coated article, wherein, have the described multilayer film of claim 1 or 2 on coated article.

4. coated article as claimed in claim 3, wherein, above-mentioned coated article is plastics.